Surface active agent



Patented Apr. 27, 1943 STATES amass TENT SURFACE acrrva AGENT HillaryRobinette, Terre Haute, Ind, asslgnorto Commercial Solvents Corporation,Terre Haute, .Ind., a corporation of Maryland No Drawing.

4 Claims,

wherein It represents an alkyl group having at least fivecarbon atoms.

As specific examples of the substituted 1.3- dioxanes which are includedby the above generic formula,, there may be mentioned -amino -2- (3-pentyl) '-5-hydroxymethyl-1,3-dioxane, 5-amino-'2-hexyl-5-hydroxymethyl-1,3-dioxane, 5-amino- 2-(3-heptyl)-5-hydroxymethyl-1,3-dioxane, 5- amino-2-hendecyl-5-hydroxymethyl-1,3-dioxane,

- 5-amino-2-octyl-5 hydroxymethyl-1,3-dioxane,,

and the like.

' In numerous industries there exists a need for certain types ofchemical compounds ordinarily employed in small quantities, to secure anefiect which is principally the result of a wetting ac- Specifically,these compounds" tion, such as the effect obtained by the presence of asurface active agent at a water oil interface. For example, in thetextile and leather-treating industries, there are many situations wherewetting or detergent action is vhighly desirable; as aresult, manydifferent agents have been proposed to reduce surface tension andpromote wetting". The materials that have been employed in the past,however, although satisfactory in some respects, have not met withunqualified success in all cases.

The ordinary soaps, although their surface active properties have longbeen recognized, are deficient in many respects when employed in thefield'of detergent and wetting agents. For example, although soaps actemciently as detergents in weakly alkaline solutions, they are of novalue for this purpose in acid solutions since under such circumstancesthe free fatty acids,

which is insoluble in water, is liberated. In'

strongly alkaline solutions, on the other hand, ordinary soapsbecomeinsoluble and are salted out of solution. In addition, in thepresence of Application November 15, 1941, I Serial No. 419,317

solutions containing calcium or magnesium salts, such as ordinary hardwater, the fatty acid present in the soap is precipitated as a calciumor magnesium soap, such soaps being insoluble, sticky materials, which,rather than having any detergent action, are regarded as undesirableimpurities in solutions employed in the textile and related industries.

In an effort to furnish materials to such industries, free from theundesirable properties of ordinary soaps, there have been developed asdetergent and wetting agents, products obtained by the sulfonation ofcertain fatty acids occurring in oils and fats. Such fatty acids arecharacterized by containing unsaturated linkages and/or hydroxyl groupsin the molecule. On sulfonating such acids, products are obtained whichcontain sulfuric acid ester groups in the molecule, and of coursecarboxylic acid groups are attached to the terminal carbon atoms. Theproducts, however, in general possess weaker wetting and detergentproperties than soaps. Such products are also relatively unstable andare capable of being decomposed by hydrolysis.

Other proposed wetting agents comprise the semiand completely-esterifiedproducts resulting from the esterification of a higher alcohol with anunsaturated polybasic acid. After the unsaturated esterlfied acid isproduced, it is converted into a more soluble form,- ordinarily bytreatment with sodium bisulfite to yield'the corresponding sulfoderivative of the esterified polybasic acid. While such materials havemet with a considerable degree of success in various in- 5 35 dustrieswhere the need for surface-active materials exists, they are not withoutcertain defects. Obviously surface-active agents of this type are notstable to alkali and in some instances, especially in the textile field,much difficulty has been experienced with the tendency of the textiletreating baths containing such materials, to foam.

I have now discovered that aminodioxanes of the class included by theabove structural formula serve as highly satisfactory wetting agents,particularly where prior wetting and detergent agents, especially of thetype mentioned above, are of littleor no value. For example, the wettingagents of the present invention are not decomposed either by hardwaters, or solutions containing appreciable quantities of alkali. My newwetting agents possess the further advantage in that aqueous solutionsthereof do not foam. In addition, these materials. which are water-whiteliquids, are soluble in most of the common organic solvents.

In general, the quantity of the new wetting agents which may be employedwill be found to vary with the type of wetting operation underconsideration, as well as with the material to be wetted. For mostpurposes, however, I have found that these wetting agents may beutilized in amounts of from about 0.15 to 0.60 per cent by weight of thetreating bath. In this connec tion, I have found that in many cases itmay be desirable to employ a solubilizing material with the Wettingagents of the present invention. In such instances, the quantity ofwetting agent employed may be reduced, depending of course upon'thequantity and type of solubilizing agent employed. Suitable solubilizingmaterials which may be utilized in combination with my wetting agents,are sulfonated castor oil, sulfonated pctroleum oils, sulfonated alkylaromatic compounds, sulfated esters, sulfated ether-alcohols, sulfonatedalkyl diphenyls, soaps and the like.

The wetting power of certain of the aminodioxanes of the presentinvention is demonstrated by the data appearing in the table below, andwas measured by the method of Draves and Clarkson (Am. Assoc... TextileColorists and Chemists Year Book, v01. 17, pp. 216-222 (1940)), whichdetermines the sinking time required for a gram skein of unboiled 2-ply'cotton yarn in varying concentrations of aqueous solutions of theaminodioxanes at a temperature of 30 C.

Table rams of 'q k ammo in mg Ompmmd dioxane L time per liter 5-amino-2-(3-amy1)-5-hydroi;ymethyl-l 3- Seconds dioxane 1 6 275-amino-2-hexyl-5-hydro met ,3-

dioxane 3 1. 5 150 5-llXIllll0 -2- (3-heptyl) 5 hydroxymethyl-1.3-dioxanc 2 3 l {I 1 Instantaneous.

The wetting agents of the present invention may be prepared inaccordance with any of several suitable procedures. I prefer, however,to produce such materials by means of the process described in U. S.Patent No. 2,247,256 granted June 24, 1941, to Murray Senkus. In aprocedure of this character, the corresponding nitrodioxane is subjectedto high-pressure hydrogenation in the presence 'of a. nickel catalystand a suitable solvent such as methanol, at a temperature in theneighborhood of -30 C. The starting materials in this process areconveniently prepared by condensing tris(hydroxymethyl) -nitromethanewith any of a number of suitable aldehydes, such as hexanahheptanal,2-ethylhexanal, dodecanal, and the like. This condensation reaction iscarried out by heating tris(hydroxymethyl)nitromethane in the presenceof the desired a1dehyde and a small quantity of an acid catalyst; and,if desired, in the presence of an organic liquid, such as benzene ortoluene, which is capable of removing the water produced during thereaction in the form of a constant boiling mixture.

With reference to the compounds covered by certain of the species claimsherein, these materials, .i. e., 5-amino-2-hexyl-5-hydroxymethyl- 1,3-dioxane and 5-amino-2(3-heptyl) -5-hydroxymethyl-1,3-dioxane, maybesynthesized by first of a suitable nickel catalyst, such as Raney.

nickel.

It is understood that applicant does not claim the amino dioxanes per sedisclosed and referred to herein, but instead, claims merely a new andnovel use of said compounds.

As previously stated, the wetting agents of' the present invention maybe used alone or in combination with certain solubilizing agents, orother detergents, for cleansing and securing vegetable and animal fiberswhen removing fatty or oily materials therefrom. They may also be usedas penetrants in flax-retting baths. The

penetrating power of these new compositions may be utilized withadvantage when said compositions are added to baths containing starchyferments which are employed for removingsizing from textile materials.These products function as useful wetting, cleansing and penetratingagents in bleaching liquors, such as those used in the kier boiling ofcotton goods, and may be added to the lye liquors used for mercerizingcotton goods. They can also be used to assist in twist setting of yarnand in processes of stripping colors. Such compounds may also be used asassistants in processes of stripping dyes from dyed textile material.

A second class of uses of these new surface- ,active agents is asassistants in the application of dyestuffs. They may be used as dyelevelingagents due to their wetting and penetrating properties inneutral or alkaline dyeing baths, and are capable of facilitating dyeingwith developed dyes, the dyeing of acetate fibers with insoluble. dyes,the dyeing of animal fibers with vat-dyes, the dyeing of varioussynthetic fibers, and. the dyeing of leather.

It will readily be seen from the foreging discussion that by means ofthe present invention a large group .of new. surface-active materialshas been made available, and that suchagents are adapted for use innumerous industrial processes which require surface-active substances.It will also be apparent to those skilled in the art that many widelydifferent embodiments of the present invention exist, and that suchembodiments may be utilized without departing from the scope of saidinvention.

My invention now having been described, what I claim is:

1. In the process for the wet treatment of organic fibrous materials inan aqueous bath, the improvement which comprises incorporating in thebath in an amount to change its surface wherein R represents'an alkylgroup having at.

least five carbon atoms.

2. In the process for the wet treatment of organic fibrous materials inan aqueous bath, the step which comprises incorporating in the bath inamounts of from about 0.15 to 0.60 per cent by weight of the finalsolution, an aminodloxane having the formula:

